DE2739953A1 - DOUBLE TRIPHENYLMETHANE DYES - Google Patents

Description

O.Z. 32 775

Doubled triphenylmethane dyes The invention relates to compounds of the general formula I.

in the

B a pontic, the best

B independently of one another hydrogen or optionally substituted alkyl, two beds B together with the nitrogen one heterocyclic saturated 5- or 6-bing and the best

B independently of one another hydrogen or C.- to C.-alkyl,

B independently of one another is hydrogen, C ₁ - to C-alkyl or halogen X is an anionic best.

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The beds B can be the same or different; they generally have 1 to 8 carbon atoms and can be replaced, for example, by hydroxy, C. to C. alkoxy, C. ₁ to C. alkanoyloxy, C. to C. alkoxycarbonyl, cyano, chlorine, acetyl, acetylamino or phenyl.

Individual bests are for example: CH-, CpH _1. , C, H_, CH-, C ₁ -H ₁₁ , C ₆ H ₁₃ , C ₈ H ₁₇ , C ₂ H ₄ OH, CH ₂ CHOHCH ₃ , CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OC ₂ H ₅ ,

CH ₂ CH ₂ OC ₄ H ₉ , CH ₂ CHCH ₃ , CH ₂ CH ₂ OCOCH ₃ , CH ₂ CH ₂ OCOC ₂ H ₅ , CH ₂ CH ₂ COOCH ₃₁ OCH ₃

CH ₂ CH ₂ COOC H, CH ₂ CH ₂ CN, CHgCHgCl, CH ₂ CH ₂ COCH ₃ , CHgCHgCHgNHCOCHj CH ₂ C ₆ H ₅ .

Cyclic Best -N. are e.g. ~ \ J »" ^ \ / »" ^

or -

Preferred best B are hydrogen, methyl and ethyl B is preferably hydrogen and, as alkyl, methyl,

2 B is preferably hydrogen, methyl as alkyl, or chlorine.

In particular, best of the formula are used as bridge links B.

) _n -, -CH ₂ -Ar-CH ₂ -, Β _{θ φ} Β

-C ₂ H ₄ -N- (CH ₂ ) _n -NC ₂ H ₄ -,

-C ₂ H ₄ -N-CH ₂ -Ar-CH ₂ -NC ₂ H ₄ -, -C ₂ H ₄ -NC ₃ H ₄ - or

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90981 2/0043

-C ₂ H ^ OCONH-Ar-NHCOOC ₂ H ^ -, where Ar phenylene, diphenylene or naphthylene optionally substituted by chlorine, methyl or methoxy and the numbers 2 to 8 and Q are methyl, ethyl or benzyl and R is the indicated Has meaning.

The moiety -ff-B-N- can also be the preferred radical -

TJ

represent.

To prepare the compounds of the formula I, compounds of the formula II R ² R ²

I I '

II

k '

with compounds of the formula III

R ¹ R ¹

III

according to the German patent specification 2 152 703, the German Auslegeschrift 2 334 918 and German Offenlegungsschrift 2 427 606 implement the procedure described. Compared to the processes described, there are no special features in the reactions, the reactions run analogously.

As a further method for the preparation of the compounds of the formula I can the compounds of the formula II are used according to methods known in the art with compounds of the formula IV

condense.

'R

R ¹ R ¹

909812/0043

IV

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ORIGINAL INSPECTED

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Compounds of the formula II can be obtained by reacting compounds the formula

Hal-B-Hal

with compounds of the formula

VV- N or v \ - NCH. N

manufacture according to methods known at calibration. Connections with the Pontic

-C ₀ H-OCONH-Ar-NHCOOC ₀ H. -2 4 2 4

obtained by reacting bis-isocyanates with the corresponding Hydroxy compounds. Compounds of the formula I are violet to reddish-tinged blue and are particularly suitable as basic dyes for dyeing paper, preferably bleached sulphite pulp The dyes have considerable substantivity and are largely exhaustive from aqueous staining medium; they are therefore very environmentally friendly «

-8th-

909812/0043

O. ζ. 32 775

Compounds of the formula Ia are of particular industrial importance

k '

in the

- or C ₂ H ₄ OCONH

the best A methyl or ethyl,

A is hydrogen or methyl and

B ¹ - (CH ₂ ) _p -, -CI

mean, where ρ means the numbers 2 to 6 and the Best

HB ¹ -NA

the best can be.

-O-

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example 1

A mixture of 357 parts of Ν, Ν'-diphenylpiperazine, 762 parts 4,4-bisdimethylaminodiphenylmethane, 1460 parts glacial acetic acid, 10 parts Chloranil and 10 parts of the Fe complex of DihydrodibenzotetraazafHjannulens is at 40-50 C with vigorous stirring 96 parts of oxygen oxidized.

It will show approx. 27OO parts of an approx. 45 liquid setting of the dye of the formula

obtained that dyes bleached sulfite pulp purple.

Example 2

A mixture of 508 parts of 4 »4'-bisdimethylaminodiphenylmethane, 344 parts of 1,4-bis (N-phenyl-N-ethylaminomethyl) benzene, 1500 parts of glacial acetic acid, 10 parts of chloranil and 10 parts of the co-complex of Mhydrodibenzotetraaza [i43annulens is used in ^{35-45 0} C with intensive blistering by the introduction of air so long as oxidized until no more oxygen consumption is determined.

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There are 2500 parts of an approx. 45% liquid adjustment of the color substance of the formula

obtained that dyes bleached sulfite pulp purple.

Example 3

A mixture of 508 parts of 4,4'-bisdimethylaminodiphenylmethane, 372 parts of 1,4-BiS- (NO-tolyl-N-ethylaminomethyl) benzene, 1200 parts of glacial acetic acid, 300 parts of propylene glycol, 10 parts of chloranil and 10 parts of the Fe complex des Dihydrodibenzotetraaza £ 14]] annulenB is oxidized at 35 -43 ⁰ C and intensive charging by passing in air until no more oxygen consumption can be determined. Approx. 2400 parts of an approx. 45 # liquid formulation of the dye of the formula are used

Me _n N

obtained, which gives the bleached sulfite pulp a reddish blue color.

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In the following table the structure of the dianilines (Η-B) is given, those with 4> 4 ^I- bis-dimethylaminodiphenylmethane according to the details of Examples 1-3 to further dyes of the formula

NHe.

U ₊

η = 0 -

NMe,

can be oxidized.

H ₂ B or H ^ B ** ⁷ "IX?

η = 1 and 2

Shade of the dye on bleached sulphite " cellulose

CH

CgH.CN

CH_

violet

reddish blue

violet

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ORIGINAL INSPECTED

-ίσ . ζ. 32 775

x?> N-CH.

CVSC ₂ H ₄ -H- ^

? 2 ^H 5

^{Ε Η}

V ^ V-N

C_H _C I ² 5

CH,

CH CH,

? ^Η

5 f »

CH,

^ fA Φ? ^Η 3 ® <i ^H 3? 2%

Vf VNC ₀ H.-NH _r> C-CH = CH-CH _o -N- ^ C_H _{> l} -N- / rv \ ^ = 'Z 4 I 2 ^ 1 ^ 4 \ - /

CH ₃ CH ₃

C ₀ H, - CH, CH 2 5 φ | 3

CH,

he violet

reddish blue

violet

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° 2 ^H 5

Cl «

CH,

€ Γ3? 2 ^Η 5 -NC ₂ H ₄ -N- ^

CHj

^C 2 ^H 5 ©? 2 ^Η 5

^C 2 ^H 5

Θ? 2 ^Η 5

³ 2-f- ^C 2 ^H 4 "C,

? ₂ a

violet

reddish blue

violet

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ORIGINAL INSPECTED

O.Z. 32 775

Example 4

A mixture of 282 parts of 4,4'-bisäthylamino-3,3 ^l -dimethyldiphenylmethane, 238 parts of Ν, Ν'-diphenylpiperazine, 800 parts of glacial acetic acid, 5 parts of chloranil and 5 parts of the Fe-Eomplezes of Sihydrodibenzotetraazafi4iannulens is at 40-50 ° C is oxidized with air until no more oxygen uptake can be detected. Approx. 1350 parts of an approx. 40 # liquid setting of the Dye of the formula

H CH,

\ _ / ^H 3 ^C , H
I. • Λ * ^N " ^CH 3 L. I. ^ N-CH,
I 3 HO H

obtained that dyes bleached sulfite pulp red-violet.

Example 5

A mixture of 310 parts of 4,4'-bisdiethylaminodiphenylmethane, 238 parts of N.IJt-diphenylpiperazine, 600 parts of glacial acetic acid, 200 parts Propylene glycol, 5 parts of chloranil and 5 parts of the Fe complex des Dihydrodibenzotetraaza £ i4] annulens and is at 40-50 C with 64 parts of oxygen oxidized.

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Approx. 1380 parts of an approx. 40 $ liquid setting of the Dye of the formula

H ₅ C ₂ -N

obtained that dyes bleached sulfite pulp purple.

BASF Aktiengesellschaft / j

909812/0043

Claims (1)

BASF Akoiengesellschax't Our reference: CZ. 32 775 Bg / Pe 6700 Ludwigshafen, 01.09-1977 Claims 1. Doubled triphenylmethane dyes of the general formula in the B a pontic, the best R independently of one another hydrogen or optionally s-abü ^ itü- iertee alkyl, two radicals R together with the nitrogen a heterocyclic saturated 5- or 6-ring and the radicals H ¹ independently of one another hydrogen or C ₁ - bi3 C.-alkyl, R ² independently of one another hydrogen, C.- to C.-alkyl or Udo each ;: X is an anionic radical. 2. Dyestuffs according to Claim 1 of the formula 408 / Γ7 Il V ^A 909812/0043 • A A -2- BATH ORIGINAL -2- O. line 32 in the the best A is methyl or ethyl, A is hydrogen or methyl and B ¹ - (CH-) -, -CH _o - ^^ - CH "- or C ₀ H, OCGEH - ^" ^ - HEOOOC ₀ E. mean, where ρ means the numbers 2 to 6 and the nest HB ¹ -U- I A the best AJ- can be. ">. Process for the preparation of dyes according to Claim 1, characterized in that compounds of the formula II r, 2 "2 B 2 with compounds of the formula III ¹ H ¹ Reacts under oxidizing conditions or that compounds of the Formula II with compounds of the formula 909812/0043 ORIGINAL INSPEOTED O. Z. 52,775 R ¹ condensed. 4. The use of the compounds according to claim 1 for dyeing Paper. -4- 909812/0043